JP2009203270A - Polycarbonate resin composition having excellent appearance - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition having excellent impact characteristics, excellent moldability, and excellent appearance free from a flow line formed in a weld portion or an unevenly thick portion. <P>SOLUTION: Provided is the polycarbonate resin composition comprising 99 to 1 wt.% of an aromatic polycarbonate resin (component A) and 1 to 99 wt.% of a graft copolymer (component B) comprising a rubbery polymer in which rubber particles have a weight-average particle diameter of 0.20 to 2.0 μm, a vinyl cyanide monomer and an aromatic vinyl monomer in a (A)+(B) total amount of 100 pts.wt., 0.1 to 10 pts.wt. of a core-shell type graft copolymer (component C) obtained by copolymerizing an alkyl (meth)acrylate monomer or a mixture of the alkyl (meth)acrylate monomer with a copolymerizable monomer in the presence of a dienic rubber component having a weight-average particle diameter of 0.30 to 0.50 μm by an emulsion polymerization method, preferably further 0.01 to 25 pts.wt. of at least one flame retardant (component E) selected from the group consisting of organic phosphorous flame retardants, organic metal salt-based flame retardants, and silicone-based compounds, and 0.05 to 2 pts.wt. of a fluorine-containing anti-dropping agent (component F). The polycarbonate resin composition has excellent impact characteristics, excellent moldability, and excellent appearance free from a flow line formed in a weld portion or an unevenly thick portion. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a polycarbonate resin composition having excellent appearance and a molded product thereof. More specifically, by using a resin composition containing a polycarbonate resin, a specific graft copolymer, and a specific core-shell type graft copolymer, an excellent appearance without a flow line generated in a weld portion or an uneven thickness portion is obtained. The present invention relates to a polycarbonate resin composition having excellent impact characteristics and moldability, and a molded product thereof.

  Polymer alloy of aromatic polycarbonate resin and graft copolymer represented by ABS resin has excellent moldability and high impact characteristics, and is used in a wide range of applications such as office equipment, electrical and electronic equipment, and automobiles. Is used. In particular, office equipment such as laser beam printers, copiers, notebook computers and projectors, and housings for electrical and electronic equipment have strong demands for high impact and excellent moldability. Polymer alloys made of polymers are the mainstream.

  More recently, housing moldings have been made thinner and less painted for the purpose of weight reduction and cost reduction. As a result, the demand for housing materials with high appearance and high impact is increasing. .

  As such a housing material, many methods for adding a core-shell type graft copolymer to a polymer alloy of a graft copolymer represented by an aromatic polycarbonate resin and an ABS resin have already been proposed, and a wide range of related knowledge is available. Are known.

  For example, by blending an MBS resin as a core-shell type graft copolymer into a resin composition comprising an aromatic polycarbonate, AS resin, ABS resin, or organophosphorus compound oligomer, a polycarbonate system having excellent fluidity, impact characteristics, and heat resistance It is already known that a flame retardant resin composition can be obtained. (Patent Document 1, Patent Document 2, Patent Document 3) However, in the case of such a polycarbonate-based flame retardant resin composition, high impact is maintained while maintaining high fluidity by blending an MBS resin as a core-shell type graft copolymer. Although it is possible to obtain strength, linear color unevenness due to the flow pattern during injection molding occurs at uneven parts such as welds, ribs, and bosses of molded products, which is a major problem in appearance. It has become. This is because the morphological state of a molded product made of such a polycarbonate-based flame retardant resin composition differs depending on where the flow pattern changes such as a welded portion or an uneven thickness portion, and is representative of aromatic polycarbonate resin and ABS resin. Many methods have already been proposed for improving the compatibility of graft copolymers.

For example, by adding a terpene resin as a compatibilizer to a composition comprising a styrene resin such as an ABS resin and a HIPS resin in a polycarbonate resin, a polycarbonate heat excellent in weld strength, weld appearance, and melt fluidity It is already known that a plastic resin can be obtained. (Patent Document 4) However, when such a compatibilizer such as a terpene resin is used, it is less effective as a countermeasure against poor appearance of color unevenness due to a flow pattern during injection molding, and a decrease in combustibility. There are problems such as being seen.
As described above, there is a demand for a resin material having a higher level of appearance and impact characteristics, but it has not been obtained.

WO2000 / 001839 Publication JP 2003-41114 A JP 2001-302898 A JP 2000-63651 A

  In view of the above, an object of the present invention is to provide a polycarbonate-based resin composition having an appearance improved to a higher level and a high impact property while maintaining its inherent flame retardancy, heat resistance, and fluidity. is there.

  As a result of intensive studies to solve the above problems, the present inventor blended a core-shell type graft copolymer having a specific weight average rubber particle diameter with a graft copolymer represented by an aromatic polycarbonate resin and an ABS resin. As a result, it was found that the appearance defect problem caused by the polymer alloy morphology of the graft copolymer represented by the aromatic polycarbonate resin and the ABS resin can be solved, and the present invention has been completed.

  According to the present invention, the above-mentioned problem is that the aromatic polymer resin (component A) is 99 to 1% by weight, the rubber polymer having a weight average particle diameter of rubber particles of 0.20 to 2.0 μm, vinyl cyanide single A diene rubber having a weight average particle diameter of 0.30 to 0.50 μm with respect to 100 parts by weight in total of 1 to 99% by weight of a graft copolymer (component B) containing a monomer and an aromatic vinyl monomer Core-shell type graft copolymer obtained by copolymerizing an alkyl (meth) acrylate monomer or a mixture of an alkyl (meth) acrylate monomer and a copolymerizable monomer in the presence of a component by an emulsion polymerization method This is achieved by a polycarbonate resin composition containing 0.1 to 10 parts by weight of (Component C).

  One of the preferred embodiments of the present invention is that (2) a graft copolymer (component B) is obtained by emulsion polymerization and contains 1 to 40% by weight of a diene rubber as a rubbery polymer. It is a polycarbonate resin composition of the said structure (1) which is.

  One of the preferred embodiments of the present invention is (3) the above structure wherein the core-shell type graft copolymer (component C) is a core-shell type graft copolymer containing 40 to 90% by weight of diene rubber component ( The polycarbonate resin composition of 1) or (2).

  According to another aspect of the present invention, (4) the above-mentioned constitutions (1) to (1) containing 0.1 to 50 parts by weight of the inorganic filler (D component) with respect to 100 parts by weight of the total of the A component and the B component. The polycarbonate resin composition according to any one of 3).

  One of the preferred embodiments of the present invention is the above-mentioned constitutions (1) to (4), wherein (5) the inorganic filler (component D) is one or more selected from the group consisting of talc, mica, and wollastonite. Any of the polycarbonate resin compositions.

  Moreover, according to another aspect of the present invention, (6) from the group consisting of phosphate ester, alkali (earth) sulfonate metal salt, and silicone compound with respect to 100 parts by weight of component A and component B in total. The above-described constitutions (1) to (1) containing 0.001 to 25 parts by weight of one or more selected flame retardants (E component) and 0.05 to 2 parts by weight of a fluorine-containing anti-dripping agent (F component). The polycarbonate resin composition according to any one of 5).

  One of the preferred embodiments of the present invention is the polycarbonate resin according to any one of the above constitutions (1) to (6), wherein (7) the flame retardant (component E) is a phosphate ester represented by the following formula (I): It is a composition.

（式中のＸは、ハイドロキノン、レゾルシノール、ビス（４−ヒドロキシジフェニル）メタン、ビスフェノールＡ、ジヒドロキシジフェニル、ジヒドロキシナフタレン、ビス（４−ヒドロキシフェニル）スルホン、ビス（４−ヒドロキシフェニル）ケトンおよびビス（４−ヒドロキシフェニル）サルファイドからなる群より選ばれるジヒドロキシ化合物より誘導される二価フェノール残基であり、ｎは０〜５の整数であり、またはｎ数の異なるリン酸エステルの混合物の場合はそれらの平均値であり、Ｒ^４、Ｒ^５、Ｒ^６、およびＲ^７はそれぞれ独立したフェノール、クレゾール、キシレノール、イソプロピルフェノール、ブチルフェノールおよびｐ−クミルフェノールからなる群より選ばれるアリール基より誘導される一価フェノール残基である。）

(X in the formula is hydroquinone, resorcinol, bis (4-hydroxydiphenyl) methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone and bis (4 -Hydroxyphenyl) a dihydric phenol residue derived from a dihydroxy compound selected from the group consisting of sulfides, n is an integer from 0 to 5, or in the case of a mixture of n different phosphate esters, R ⁴ , R ⁵ , R ⁶ , and R ⁷ are average values each derived from an aryl group selected from the group consisting of independent phenol, cresol, xylenol, isopropylphenol, butylphenol, and p-cumylphenol. Residual phenol Group.)

Details of the present invention will be described below.
(Component A: aromatic polycarbonate resin)
The polycarbonate resin as the component A of the present invention is an aromatic polycarbonate resin obtained by reacting a dihydric phenol and a carbonate precursor. The reaction methods include an interfacial polycondensation method, a melt transesterification method, and a carbonate prepolymer. Solid phase transesterification method, and ring-opening polymerization method of a cyclic carbonate compound.

  Representative examples of dihydric phenols include hydroquinone, resorcinol, 4,4'-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol) A), 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) pentane, 4,4 '-(P-phenylenediisopropylidene) diphenol, 4,4'-(m-phenylenediisopropylidene) diph 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (4- Hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ester, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, bis (3,5-dibromo- 4-hydroxyphenyl) sulfone, bis (4-hydroxy-3-methylphenyl) sulfide, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, etc. Is mentioned. A preferred dihydric phenol is bis (4-hydroxyphenyl) alkane, and bisphenol A is particularly preferred from the viewpoint of impact resistance.

  As the carbonate precursor, carbonyl halide, carbonate ester, haloformate or the like is used, and specific examples include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and the like.

  In producing a polycarbonate resin by the interfacial polymerization method using the dihydric phenol and the carbonate precursor, a catalyst, a terminal terminator, an antioxidant for preventing the dihydric phenol from being oxidized, and the like as necessary. May be used. The polycarbonate resin of the present invention is a branched polycarbonate resin copolymerized with a trifunctional or higher polyfunctional aromatic compound, or a polyester carbonate resin copolymerized with an aromatic or aliphatic (including alicyclic) difunctional carboxylic acid. A copolymer polycarbonate resin copolymerized with a bifunctional alcohol (including an alicyclic group), and a polyester carbonate resin copolymerized with the bifunctional carboxylic acid and the bifunctional alcohol together. Moreover, the mixture which mixed 2 or more types of the obtained polycarbonate resin may be sufficient.

  Examples of trifunctional or higher polyfunctional aromatic compounds include 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane. Can be used.

  When a polyfunctional compound that produces a branched polycarbonate is included, the ratio is 0.001-1 mol%, preferably 0.005-0.9 mol%, particularly preferably 0.01-0, based on the total amount of the aromatic polycarbonate. 0.8 mol%. In particular, in the case of the melt transesterification method, a branched structure may occur as a side reaction. The amount of the branched structure is also 0.001 to 1 mol%, preferably 0.005 to 0.005% in the total amount of the aromatic polycarbonate. Those having 9 mol%, particularly preferably 0.01 to 0.8 mol% are preferred. Such a ratio can be calculated by 1H-NMR measurement.

The aliphatic bifunctional carboxylic acid is preferably α, ω-dicarboxylic acid. Examples of aliphatic difunctional carboxylic acids include sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, icosanedioic acid, and other straight-chain saturated aliphatic dicarboxylic acids, and cyclohexanedicarboxylic acid. Preferred are alicyclic dicarboxylic acids such as As the bifunctional alcohol, an alicyclic diol is more preferable, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecane dimethanol.
Further, a polycarbonate-polyorganosiloxane copolymer obtained by copolymerizing polyorganosiloxane units can also be used.

  The aromatic polycarbonate resin is a mixture of two or more of the above-mentioned various aromatic polycarbonates such as polycarbonates having different dihydric phenols, polycarbonates containing branched components, various polyester carbonates, and polycarbonate-polyorganosiloxane copolymers. It may be. Furthermore, what mixed 2 or more types can also be used about various types, such as the polycarbonate from which the manufacturing method shown below differs, and the polycarbonate from which a terminal stopper differs.

  The reaction forms such as interfacial polymerization, melt transesterification, solid phase transesterification of carbonate prepolymer, and ring-opening polymerization of cyclic carbonate compounds, which are methods for producing the polycarbonate resin of the present invention, are various documents and patent publications. This is a well-known method.

The molecular weight of the aromatic polycarbonate resin is not specified, but if the molecular weight is less than 1.0 × 10 ^4, it is difficult to obtain a sufficient strength as a molded product, and if it exceeds 5.0 × 10 ⁴ , the moldability deteriorates. Therefore, the viscosity average molecular weight is preferably 1.0 × 10 ^{4 to} 5.0 × 10 ⁴ , more preferably 1.4 × 10 ^{4 to} 3.0 × 10 ⁴ , and still more preferably 1. There are 4 × 10 ^{4 to} 2.4 × 10 ⁴ . Also, two or more aromatic polycarbonate resins may be mixed. In this case, it is naturally possible to mix with an aromatic polycarbonate resin having a viscosity average molecular weight outside the above range.

In particular, a mixture with an aromatic polycarbonate resin having a viscosity average molecular weight exceeding 5.0 × 10 ⁴ has high entropy elasticity, and has a characteristic that appearance defects of molded products due to rheological behavior represented by jetting are not likely to occur. When such an appearance defect occurs, it is an appropriate mode. Further, the gas injection amount is stable in gas injection molding and the like, and in the foam molding, the foamed cells are stable, and fine and homogeneous cells are easily formed.

More preferably, it is a mixture with a polycarbonate resin having a viscosity average molecular weight of 8.0 × 10 ⁴ or more, and further preferably a mixture with a polycarbonate resin having a viscosity average molecular weight of 1.0 × 10 ⁵ or more. That is, those capable of observing a molecular weight distribution of two or more peaks in a measuring method such as GPC (gel permeation chromatography) can be preferably used.

The viscosity average molecular weight referred to in the present invention is first determined by using an Ostwald viscometer from a solution in which 0.7 g of a polycarbonate resin is dissolved in 100 ml of methylene chloride at 20 ° C., as calculated by the following formula:
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]
The obtained specific viscosity is inserted by the following equation to determine the viscosity average molecular weight M.
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7

(B component: Graft copolymer)
The graft copolymer of the present invention is a graft copolymer containing a rubbery polymer having a weight average particle diameter of 0.20 to 2.0 μm, a vinyl cyanide monomer and an aromatic vinyl monomer. Say.

  The rubbery polymer referred to in the present invention is a polybutadiene, a diene copolymer (for example, a random copolymer or block copolymer of styrene / butadiene, an acrylonitrile / butadiene copolymer, and a (meth) acrylic acid alkyl ester. And butadiene copolymers), polyisoprene, copolymers of ethylene and α-olefins (eg, ethylene / propylene random copolymers and block copolymers, ethylene / butene random copolymers and block copolymers) A copolymer of ethylene and an unsaturated carboxylic acid ester (for example, ethylene / methacrylate copolymer and ethylene / butyl acrylate copolymer), a copolymer of ethylene and an aliphatic vinyl (for example, ethylene)・ Vinyl acetate copolymer, etc.), ethylene and propylene Non-conjugated diene terpolymers (eg, ethylene / propylene / hexadiene copolymers), acrylic rubbers (eg, polybutyl acrylate, poly (2-ethylhexyl acrylate), and copolymers of butyl acrylate and 2-ethylhexyl acrylate) Polymers, etc.), as well as silicone rubber (eg, polyorganosiloxane rubber, IPN type rubber comprising a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component; that is, the two rubber components cannot be separated from each other. And rubber having an intertwined structure, and an IPN type rubber comprising a polyorganosiloxane rubber component and a polyisobutylene rubber component. Of these, polybutadiene, diene copolymer, polyisoprene, acrylic rubber, ethylene and propylene and non-conjugated diene terpolymers, which are more effective, are particularly suitable. Polymers are preferred.

  The weight average particle diameter of rubber particles of such a rubbery polymer is in the range of 0.20 to 2.0 μm, preferably 0.25 to 1.5 μm, more preferably 0.28 to 1.3 μm. When the weight average particle diameter of the rubber particles is smaller than 0.20 μm, the impact improving effect due to the addition of the graft polymer is lowered, which is not preferable. On the other hand, if it exceeds 2.0 μm, the dispersion state with the polycarbonate resin is poor and impact reduction is caused, which is not preferable.

  The weight average particle diameter of the rubber particles in the present invention is a value measured by a transmission electron microscope. Specifically, a drop of the emulsion-like rubber-like polymer was taken on a mesh for transmission electron microscope measurement and dyed with osmium tetroxide or ruthenium tetroxide vapor. Next, a dyed rubber-like polymer sample was photographed with a transmission electron microscope (TECNAI G2 manufactured by FEI, acceleration voltage 120 kv), and image processing software (Nexus NewQube) was used from 200 rubber particles in the photographed image. The weight average particle size was calculated.

Examples of the vinyl cyanide monomer referred to in the present invention include acrylonitrile and methacrylonitrile, and acrylonitrile is particularly preferable.
Examples of the aromatic vinyl monomer in the present invention include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, vinylxylene, ethylstyrene, dimethylstyrene, p-tert-butylstyrene, vinylnaphthalene, methoxy. Examples thereof include styrene, monobromostyrene, dibromostyrene, fluorostyrene, and tribromostyrene, and styrene is particularly preferable.

  The content of the rubber component of the graft copolymer of the present invention is in the range of 1 to 40% by weight, preferably 5 to 30% by weight, and more preferably 10 to 25% by weight. If the content exceeds 40% by weight, the effect of improving fluidity becomes insufficient, which is not preferable. Moreover, when the amount of rubber is less than 1% by weight, the impact improving effect is insufficient, which is not preferable.

The graft copolymer of the present invention is not particularly specified in the production method, but those produced by an emulsion polymerization method can be preferably used.
Specific examples of the graft copolymer of the present invention include ABS resin, AES resin, ASA resin and the like, and any of them can be easily obtained. Of these, ABS resin is more preferable.
ABS resin has excellent moldability for thin-walled molded products, and also has good impact resistance. In particular, preferable characteristics are exhibited in combination with a polycarbonate resin.

  Here, the ABS resin is a graft copolymer mainly composed of acrylonitrile, butadiene rubber and styrene, the AES resin is a graft copolymer mainly composed of acrylonitrile, ethylene-propylene rubber and styrene, and the ASA resin is acrylonitrile, styrene, and A graft copolymer mainly composed of acrylic rubber is shown.

  The graft copolymers in the present invention can be used alone or in combination of two or more. For example, ABS resin and ASA resin, or ABS resin and AES resin can be used in combination. In addition, when using several graft copolymer together, content of a rubber component is 1 to 40 weight%, respectively, Preferably it is 5 to 30 weight%, More preferably, it is 10 to 25 weight%. When the content of the rubber component exceeds 40% by weight, the fluidity improving effect is insufficient, which is not preferable. Moreover, when the amount of rubber is less than 1% by weight, the impact improving effect is insufficient, which is not preferable.

ABS resin is a thermoplastic graft copolymer (ABS copolymer) obtained by graft copolymerization of a diene rubber component with a vinyl cyanide compound and an aromatic vinyl compound, and the graft copolymer and a vinyl cyanide compound. And a mixture of an aromatic vinyl compound (AS copolymer). The copolymer of the vinyl cyanide compound and the aromatic vinyl compound is used for the production of a resin comprising a thermoplastic graft copolymer obtained by graft copolymerizing a vinyl cyanide compound and an aromatic vinyl compound with a diene rubber component. It may be a copolymer produced as a by-product, or a blend of a vinyl compound copolymer obtained by separately copolymerizing an aromatic vinyl compound and a vinyl cyanide compound. The weight average molecular weight of the copolymer comprising the vinyl cyanide compound and the aromatic vinyl compound is preferably 3.0 × 10 ⁴ in a value measured in terms of standard polystyrene by GPC (gel permeation chromatography) method. in the range of to 2.0 × 10 ^5, more preferably in the range of ^{6.0 × 10 4 ~1.4 × 10 5} , more preferably of 9.0 × ¹⁰ 4 ~1.2 × ^{10 5} It is a range. The ratio of the AS copolymer can be collected by a technique such as dissolving the ABS resin in a good solvent for the AS copolymer such as acetone and centrifuging the soluble component. On the other hand, the insoluble matter (gel) becomes a net ABS copolymer.

  The ratio of the vinyl cyanide compound and aromatic vinyl compound grafted to the diene rubber component in the ABS copolymer (the ratio of the weight of the graft component to the weight of the diene rubber component), that is, the graft ratio (wt%) is 20 -200% is preferable, More preferably, it is 20-80%.

  As the diene rubber component of the ABS resin, for example, a rubber component having a glass transition temperature of −10 ° C. or less such as polybutadiene, polyisoprene, and styrene-butadiene copolymer is used.

  Examples of the aromatic vinyl compound in the ABS resin include those described above, and styrene is particularly preferable. Examples of the vinyl cyanide compound in the ABS resin include those described above, such as acrylonitrile and methacrylonitrile, with acrylonitrile being particularly preferred.

  In the ABS resin used in the present invention, the proportion of the diene rubber component in 100% by weight of the ABS resin component is preferably in the range of 1 to 40% by weight, more preferably in the range of 5 to 30% by weight, and still more preferably. It is in the range of 10 to 25% by weight, particularly preferably in the range of 12 to 22% by weight. The proportion of copolymerization of the vinyl cyanide compound and aromatic vinyl compound other than the diene rubber component is preferably 99 to 60% by weight, more preferably 95 to 70% by weight, and still more preferably 90% of 100% by weight of the ABS resin component. -75 wt%, particularly preferably 88-78 wt%. Further, the total amount of the vinyl cyanide compound and the aromatic vinyl compound is 100% by weight, the vinyl cyanide compound is 5 to 50% by weight (more preferably 15 to 35% by weight), and the aromatic vinyl compound is 95 to 50%. It is preferable that it is weight% (more preferably 65-85 weight%). Further, methyl (meth) acrylate, ethyl acrylate, maleic anhydride, N-substituted maleimide and the like can be mixed and used for a part of the components grafted to the diene rubber component, and the content ratio thereof is in the ABS resin component. What is 15 weight% or less is preferable. Furthermore, conventionally well-known various things can be used for the initiator, chain transfer agent, emulsifier, etc. which are used by reaction as needed.

In the ABS resin, the rubber particle diameter is 0.20 to 2.0 μm, preferably 0.25 to 1.5 μm, more preferably 0.28 to 1.3 μm, in terms of weight average particle diameter. As the distribution of the rubber particle diameter, either a single distribution or a rubber particle having two or more peaks can be used, and the rubber particles form a single phase in the morphology. Alternatively, it may have a salami structure by containing an occluded phase around the rubber particles.
A method for producing such an ABS resin is not particularly specified, but an ABS resin produced by an emulsion polymerization method is more preferable.

(C component: core-shell type graft copolymer)
The core-shell type graft copolymer of the present invention comprises a diene rubber component in which the weight average particle diameter of rubber particles is 0.30 to 0.50 μm, an alkyl (meth) acrylate monomer or an alkyl (meth) acrylate, and a copolymer thereof. It is a core-shell type graft copolymer obtained by copolymerizing a mixture with other monomers to be polymerized. Diene rubber typified by butadiene-styrene is mainly mixed with methyl methacrylate or methyl methacrylate and its copolymer. A copolymer obtained by graft copolymerization of a mixture with other polymerizable monomers is preferred.

  The diene rubber component used in the present invention is 50 to 100% by weight, preferably 65 to 100% by weight, more preferably 75 to 100% by weight of 1,3-butadiene as a main structural unit, and styrene copolymerizable therewith. Is a copolymer obtained by emulsion polymerization so as to be 50 to 0% by weight, preferably 35 to 0% by weight, and more preferably 25 to 0% by weight. When the amount of 1,3-butadiene as the main structural unit is less than 50% by weight, sufficient impact characteristics cannot be obtained, which is inappropriate.

  The particle size of the diene rubber component of the present invention is 0.30 to 0.50 μm, preferably 0.30 to 0.40 μm, and more preferably 0.32 to 0.38 μm in terms of weight average particle size. If the particle size of the diene rubber is less than 0.30 μm, the flow line is deeply generated at the weld and uneven thickness, and if it exceeds 0.50 μm, the dispersion will be poor and the effect as an impact modifier will be lost. It is.

  The weight average particle diameter of the rubber particles in the present invention is a value measured by the same method as the method for measuring the weight average particle diameter of the B-component rubbery polymer, and is an image of rubber particles taken by a transmission electron microscope. Is a value calculated based on

  Examples of vinyl monomers typified by styrene used to form the diene rubber component include aromatics such as styrene, α-methylstyrene, P-methylstyrene, chlorostyrene, dibromostyrene, and tribromostyrene. Examples include vinyl monomers, alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate, and alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. In addition to the above-mentioned monomers, vinyl ether monomers, vinylidene halide monomers, vinyl monomers having a glycidyl group such as glycidyl acrylate, and the like can be given.

Further, among the above vinyl monomers, those that can be crosslinkable monomers are copolymerizable with butadiene and vinyl monomers, and have two or more independent C═C bonds in the molecule. For example, aromatic polyfunctional vinyl compounds such as divinylbenzene and divinyltoluene, α, β-unsaturated carboxylic acid esters of polyhydric alcohols such as ethylene glycol dimethacrylate and 1,3-butanediol diacrylate, Allyl esters of α, β-unsaturated carboxylic acids such as trimethacrylic acid ester or triacrylic acid ester, allyl acrylate, allyl methacrylate, di- or triallyl compounds such as diallyl phthalate, diallyl sebacate, triallyl triazine, etc. Can be mentioned.
The vinyl monomer and the crosslinkable monomer can be used alone or in combination of two or more.

  Further, when forming the diene rubber component, a chain transfer agent (initiator) such as t-dodecyl mercaptan can be used in the polymerization reaction, if necessary. When the latex is prepared, the diene rubber component is added with a thickening agent to control the weight average particle diameter of the diene rubber component. Examples of such a thickening agent include inorganic salts such as sodium chloride, potassium chloride, sodium sulfate, magnesium sulfate and aluminum sulfate, organic salts such as calcium acetate and magnesium acetate, inorganic acids such as sulfuric acid and hydrochloric acid, acetic acid and succinic acid. And the like, as well as organic acid anhydrides thereof, and carboxylic acid-containing polymer latexes.

  The core-shell type graft copolymer used in the present invention comprises an alkyl (meth) acrylate monomer or an alkyl (meth) acrylate and another monomer copolymerized therewith in the latex of the diene component having the above structure. Is prepared by graft polymerization in one or multiple stages.

  That is, as a monomer used for the graft polymerization, in addition to alkyl (meth) acrylates such as methyl methacrylate and ethyl methacrylate, which are essential components, and alkyl acrylates such as methyl acrylate, ethyl acrylate and butyl acrylate, Styrene, α-methylstyrene, styrenes such as various halogen-substituted and / or alkyl-substituted styrenes, and vinyl monomers having a glycidyl group such as glycidyl acrylate, glycidyl methacrylate, and allyl glycidyl ether. Furthermore, the vinyl monomer used as the crosslinkable monomer mentioned above can be used in combination with the vinyl monomer. When mixing with the essential component alkyl (meth) acrylate, these vinyl monomers and crosslinkable monomers can be used singly or in combination of two or more.

  In the graft polymerization, the amount of the monomer or monomer mixture used is 60 to 90 parts by weight, preferably 42 to 85 parts by weight, more preferably 45 to 80 parts by weight, based on the diene rubber component latex. It is preferable that the amount be 10 parts by mass, preferably 58 to 15 parts by weight, more preferably 55 to 20 parts by weight. In addition, when using a monomer mixture, the alkyl (meth) acrylate monomer, which is an essential component, in the sum of the monomer mixture is at least 25% by weight, more preferably 40% by weight or more. Is preferred.

  The graft polymerization itself may be performed in one step by adding a monomer or monomer mixture at a time, or the monomer or monomer mixture may be added in two or more portions. However, the graft polymerization can be carried out in a plurality of stages.

  As a graft polymerization method, an emulsion polymerization means is used. When performing this graft copolymerization, as a polymerization initiator, persulfates such as potassium persulfate, ammonium persulfate, sodium persulfate, t-butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, lauroyl peroxide, diisopropylbenzene hydroperoxide, etc. Organic peroxides, azo compounds such as azobisisobutyronitrile, azobisisovaleronitrile, and the like can be used. In addition, the oxidant compound and sulfite, bisulfite, thiosulfate, first metal salt, sodium formaldehyde / sulfoxylate, dextrose, etc. may be used in combination as a redox initiator.

  The reaction temperature in graft copolymerization can be appropriately selected within the range of 40 to 80 ° C., for example, depending on the type of polymerization initiator used. Moreover, in the case of emulsion polymerization, a well-known emulsifier can be used suitably as an emulsifier with respect to a butadiene-type rubber polymer latex.

  The obtained core-shell type graft copolymer may be spray-dried (directly powdered) with or without an appropriate antioxidant and, if necessary, an additive added to the reaction solution, Alternatively, a coagulant such as an acid such as sulfuric acid, hydrochloric acid or phosphoric acid or a salt such as calcium chloride or sodium chloride is appropriately added to the reaction solution to coagulate and solidify by heat treatment. Then, after dehydration and washing, it is finally dried and used as a powder.

(D component: inorganic filler)
In the present invention, various inorganic fillers can be included as the D component. For example, talc, wollastonite, mica, clay, montmorillonite, smectite, kaolin, calcium carbonate, carbon fiber, carbon flake, carbon beads, carbon milled fiber, metal flake, metal fiber, metal coated glass fiber, metal coated carbon Fiber, metal coated glass flakes, silica, ceramic particles, ceramic fibers, ceramic balloons, aramid particles, aramid fibers, polyarylate fibers, graphite, potassium titanate whiskers, aluminum borate whiskers, basic magnesium sulfate whiskers, etc. Can be mentioned. Of these, silicate-based fillers such as talc, wollastonite, and mica are preferably used. These inorganic fillers may be used alone or in combination of two or more.

(D-1 component: talc)
Examples of the talc (D-1 component) used in the present invention include those having an average particle diameter of 5 μm or less. More preferred are those having an average particle size of 3 μm or less, particularly preferably 2 μm or less. An example of the lower limit is 0.05 μm. Here, the average particle diameter of talc refers to D50 (median diameter of particle diameter distribution) measured by an X-ray transmission method which is one of liquid phase precipitation methods. As a specific example of an apparatus for performing such a measurement, Sedigraph 5100 manufactured by Micromeritics Inc. can be cited.

  Talc is preferably used in a granulated form. As a granulation method, there are a case where a binder is used and a case where it is not substantially used. What does not use a binder is more suitable. As a granulation method when a binder is not used, a deaeration compression method (for example, a roller compression with a briquetting machine while deaeration in a vacuum state), a rolling granulation method or an agglomeration granulation method Etc.

(D-2 component: mica)
Examples of the mica (component D-2) used in the present invention include powders having an average particle diameter of 1 to 80 μm. More preferably, an average particle diameter of 2-50 micrometers can be mentioned. The average particle diameter is a value measured by a laser diffraction / scattering method. When the average particle size is 1 to 80 μm, the flame retardancy is better and the fine dispersion condition in the resin is satisfied. As the thickness of mica, one having a thickness measured by observation with an electron microscope of 0.01 to 1 μm can be used. The thickness is preferably 0.03 to 3 μm. Further, such mica may be surface-treated with a silane coupling agent or the like, and further granulated with a binder such as epoxy, urethane or acrylic, and may be granulated.

(D-3 component: wollastonite)
The wollastonite (component D-3) used in the present invention preferably has a number average fiber diameter of 0.5 to 5 μm. The number average fiber diameter is obtained by measuring a total of 1000 fiber diameters randomly extracted from an image observed with an electron micrograph and calculating the number average value. Moreover, the aspect ratio L / D (L: number average fiber length, D: number average fiber diameter) is preferably 5 or more, and more preferably 6 or more. The number average fiber length is calculated by observing wollastonite with an optical microscope or an electron microscope at a magnification at which the entire image of wollastonite can be observed almost completely, and inputting the image into an image analyzer. be able to. Examples of the image analysis apparatus include PIAS-III system manufactured by Pierce. As wollastonite used in the present invention, the loss on ignition at 1000 ° C. is preferably 2% by weight or less, more preferably 1.5% by weight or less, and further preferably 1% by weight or less.

  The polycarbonate resin composition of the present invention can contain a fold inhibitor for suppressing the breakage of the reinforcing filler. The folding inhibitor inhibits adhesion between the matrix resin and the reinforcing filler, reduces stress acting on the reinforcing filler during melt kneading, and suppresses filler folding. The effects of the crease suppressant are as follows: 1) Improved rigidity (increases the filler aspect ratio), 2) Improved toughness (when the main component is an aromatic polycarbonate resin that is easy to exhibit the toughness of the matrix resin, particularly good toughness) Effective), 3) improvement in conductivity (in the case of a conductive filler), and the like. Specifically, the crease suppressor has (i) a compound having a low affinity with the resin, and (ii) a compound having a low affinity with the resin when the compound having a low affinity with the resin is directly coated on the surface of the reinforcing filler. It is a compound having a functional group capable of reacting with the surface of the filler.

  Representative examples of the compound having a low affinity for the resin include various lubricants. Examples of the lubricant include mineral oil, synthetic oil, higher fatty acid ester, higher fatty acid amide, polyorganosiloxane (silicone oil, silicone rubber, etc.), olefinic wax (paraffin wax, polyolefin wax, etc.), polyalkylene glycol, fluorinated fatty acid. Fluorine oils such as esters, trifluorochloroethylene, and polyhexafluoropropylene glycol are listed.

  As a method of directly coating the surface of the reinforcing filler with a compound having a low affinity with the resin, (1) a method of immersing the compound directly or a solution or emulsion of the compound in the reinforcing filler; Examples include a method of passing a reinforcing filler in steam or powder, (3) a method of irradiating the reinforcing filler with powder of the compound at high speed, and (4) a mechanochemical method of rubbing the reinforcing filler and the compound. be able to.

  Examples of the compound having a structure having a low affinity with the resin and having a functional group capable of reacting with the surface of the reinforcing filler include the above-described lubricants modified with various functional groups. Examples of such functional groups include a carboxyl group, a carboxylic acid anhydride group, an epoxy group, an oxazoline group, an isocyanate group, an ester group, an amino group, and an alkoxysilyl group.

  More preferred as a folding inhibitor is a polyolefin wax having at least one functional group selected from a carboxyl group and a carboxylic anhydride group. The molecular weight is preferably 500 to 20,000, more preferably 1,000 to 15,000 in terms of weight average molecular weight. In such a polyolefin wax, the amount of carboxyl group and carboxylic anhydride group is in the range of 0.05 to 10 meq / g per gram of lubricant having at least one functional group selected from carboxyl group and carboxylic anhydride group. Is preferable, more preferably 0.1 to 6 meq / g, and still more preferably 0.5 to 4 meq / g. In the case of other functional groups, it is preferable that they are contained to the same extent as carboxyl groups.

  A particularly preferred example of the folding inhibitor is a copolymer of an α-olefin and maleic anhydride. Such a copolymer can be produced by melt polymerization or bulk polymerization in the presence of a radical catalyst according to a conventional method. Here, as the α-olefin, those having 10 to 60 carbon atoms as an average value can be preferably exemplified. More preferable α-olefins include those having an average carbon number of 16 to 60, and more preferably 25 to 55. The folding inhibitor is preferably 0.01 to 2% by weight, more preferably 0.05 to 1.5% by weight, and further 0.1 to 0.8% by weight in 100% by weight of the polycarbonate resin composition of the present invention. preferable.

(E component: flame retardant)
As the flame retardant (E component) of the present invention, various compounds conventionally known as flame retardants for aromatic polycarbonate resins can be applied. More preferably, (i) an organophosphorous flame retardant (for example, a monophosphate compound, Phosphate oligomer compounds phosphonate oligomer compounds, phosphonitrile oligomer compounds, and phosphonic acid amide compounds), (ii) organometallic salt flame retardants (for example, alkali (earth) organic sulfonate metal salts, borate metal salt flame retardants, And (iii) a silicone flame retardant comprising a silicone compound. The compounding of the compound used as a flame retardant not only improves the flame retardancy but also provides, for example, an improvement in antistatic properties, fluidity, rigidity, and thermal stability based on the properties of each compound.

(E-1) Organophosphorus Flame Retardant As the organophosphorus flame retardant of the present invention, a phosphate compound, particularly an aryl phosphate compound is suitable. Such a phosphate compound is effective in improving flame retardancy, and since the phosphate compound has a plasticizing effect, it is advantageous in that the molding processability of the resin composition of the present invention can be improved although the heat resistance is lowered. is there. As such phosphate compounds, various known phosphate compounds as conventional flame retardants can be used, and more preferably, one or more phosphate compounds represented by the following general formula (I) can be mentioned.

（式中のＸは、ハイドロキノン、レゾルシノール、ビス（４−ヒドロキシジフェニル）メタン、ビスフェノールＡ、ジヒドロキシジフェニル、ジヒドロキシナフタレン、ビス（４−ヒドロキシフェニル）スルホン、ビス（４−ヒドロキシフェニル）ケトン、およびビス（４−ヒドロキシフェニル）サルファイドからなる群より選ばれるジヒドロキシ化合物より誘導される二価フェノール残基であり、ｎは０〜５の整数、またはｎ数の異なるリン酸エステルの混合物の場合はそれらの平均値であり、Ｒ^４、Ｒ^５、Ｒ^６、およびＲ^７はそれぞれ独立したフェノール、クレゾール、キシレノール、イソプロピルフェノール、ブチルフェノール、およびｐ−クミルフェノールからなる群より選ばれるアリール基より誘導される一価フェノール残基である。）

(X in the formula is hydroquinone, resorcinol, bis (4-hydroxydiphenyl) methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, and bis ( 4-hydroxyphenyl) dihydric phenol residue derived from a dihydroxy compound selected from the group consisting of sulfides, and n is an integer of 0 to 5, or in the case of a mixture of n different phosphate esters, their average R ⁴ , R ⁵ , R ⁶ , and R ⁷ are each independently derived from an aryl group selected from the group consisting of phenol, cresol, xylenol, isopropylphenol, butylphenol, and p-cumylphenol. Divalent phenol residue .)

  The phosphate compound of the above formula (I) may be a mixture of compounds having different n numbers, in which case the average n number is preferably 0.5 to 1.5, more preferably 0.8. To 1.2, more preferably 0.95 to 1.15, and particularly preferably 1 to 1.14.

  Preferable specific examples of the dihydric phenol for deriving X in the above formula (I) include resorcinol, bisphenol A, and dihydroxydiphenyl, and among them, resorcinol and bisphenol A are preferable.

Preferable specific examples of the monohydric phenol for deriving R ⁴ , R ⁵ , R ⁶ , and R ⁷ of the above formula (I) include phenol, cresol, xylenol, and 2,6-dimethylphenol. And 2,6-dimethylphenol.

  Specific examples of the phosphate compound of the above formula (I) are mainly composed of monophosphate compounds such as triphenyl phosphate and tri (2,6-xylyl) phosphate, and resorcinol bisdi (2,6-xylyl) phosphate). Phosphate oligomers, phosphate oligomers mainly composed of 4,4-dihydroxydiphenyl bis (diphenyl phosphate), and phosphate ester oligomers mainly composed of bisphenol A bis (diphenyl phosphate) are preferred. Resorcinol bisdi (2,6- Xylyl) phosphate) -based phosphate oligomer, 4,4-dihydroxydiphenylbis (diphenylphosphate) -based phosphate oligomer, and bisphenol A bis (diphenyl) Phosphoric acid ester oligomer mainly containing Sufeto) are preferred.

  When an organophosphorus flame retardant is used as the flame retardant, the blending amount thereof is preferably 1 to 25 parts by weight, more preferably 2 to 25 parts by weight, even more preferably, based on a total of 100 parts by weight of component A and component B. Is 3 to 20 parts by weight. The effect (for example, flame retardancy etc.) expected by blending the organophosphorus flame retardant is exhibited as the preferable range is reached.

(E-2) Organometallic salt flame retardant An organic metal salt flame retardant is advantageous in that heat resistance is substantially maintained. The organometallic salt flame retardant most advantageously used in the present invention is an alkali (earth) metal sulfonate. Among them, an alkali (earth) metal salt of a fluorine-substituted organic sulfonic acid is preferable, and an alkali (earth) metal salt of a sulfonic acid having a perfluoroalkyl group is particularly preferable. Here, the carbon number of the perfluoroalkyl group is preferably in the range of 1-18, more preferably in the range of 1-10, and still more preferably in the range of 1-8.

  The metal constituting the metal ion of the fluorine-substituted organic sulfonate alkali (earth) metal salt is an alkali metal or alkaline earth metal, and examples of the alkali metal include lithium, sodium, potassium, rubidium and cesium. Examples of similar metals include beryllium, magnesium, calcium, strontium and barium. More preferred is an alkali metal. Accordingly, a preferred organometallic salt flame retardant is an alkali metal perfluoroalkyl sulfonate. Among such alkali metals, rubidium and cesium are suitable when transparency requirements are higher, but these are not versatile and difficult to purify, resulting in a disadvantage in terms of cost. is there. On the other hand, although lithium and sodium are advantageous in terms of cost and flame retardancy, they may be disadvantageous in terms of transparency. In consideration of these, the alkali metal in the perfluoroalkylsulfonic acid alkali metal salt can be properly used, but perfluoroalkylsulfonic acid potassium salt having an excellent balance of properties is most suitable in any respect. Such potassium salts and alkali metal salts of perfluoroalkylsulfonic acid composed of other alkali metals can be used in combination.

  Such alkali metal perfluoroalkylsulfonates include potassium trifluoromethanesulfonate, potassium perfluorobutanesulfonate, potassium perfluorohexanesulfonate, potassium perfluorooctanesulfonate, sodium pentafluoroethanesulfonate, perfluorobutanesulfone. Acid sodium, sodium perfluorooctane sulfonate, lithium trifluoromethane sulfonate, lithium perfluorobutane sulfonate, lithium perfluoroheptane sulfonate, cesium trifluoromethane sulfonate, cesium perfluorobutane sulfonate, cesium perfluorooctane sulfonate, Cesium perfluorohexane sulfonate, rubidium perfluorobutane sulfonate, and perful B hexane sulfonate rubidium, and these may be used in combination of at least one or two. Of these, potassium perfluorobutanesulfonate is particularly preferred.

  The organometallic salt flame retardant preferably has a fluoride ion content measured by ion chromatography of 50 ppm or less, more preferably 20 ppm or less, and even more preferably 10 ppm or less. The lower the fluoride ion content, the better the flame retardancy and light resistance. The lower limit of the fluoride ion content can be substantially zero, but is practically preferably about 0.2 ppm in view of the balance between the refining man-hour and the effect. Such alkali metal salt of perfluoroalkylsulfonic acid having a fluoride ion content is purified, for example, as follows. The perfluoroalkylsulfonic acid alkali metal salt is dissolved in 2 to 10 times by weight of the metal salt in ion-exchanged water in the range of 40 to 90 ° C. (more preferably 60 to 85 ° C.). The alkali metal salt of perfluoroalkylsulfonic acid is a method of neutralizing perfluoroalkylsulfonic acid with an alkali metal carbonate or hydroxide, or perfluoroalkylsulfonyl fluoride with an alkali metal carbonate or hydroxide. It is produced by a neutralizing method (more preferably by the latter method). The ion-exchanged water is particularly preferably water having an electric resistance value of 18 MΩ · cm or more. The solution in which the metal salt is dissolved is stirred at the above temperature for 0.1 to 3 hours, more preferably 0.5 to 2.5 hours. Thereafter, the liquid is cooled to 0 to 40 ° C, more preferably in the range of 10 to 35 ° C. Crystals precipitate upon cooling. The precipitated crystals are removed by filtration. This produces a suitable purified perfluoroalkylsulfonic acid alkali metal salt.

  When a fluorine-substituted organic sulfonic acid alkali (earth) metal salt is used as a flame retardant, the blending amount is preferably 0.01 to 1.0 part by weight based on 100 parts by weight of the total of component A and component B. More preferably, it is 0.05-0.8 weight part, More preferably, it is 0.08-0.6 weight part. The effect (for example, flame retardancy and antistatic property) expected by blending the fluorine-substituted organic sulfonate alkali (earth) metal salt is exhibited as the preferable range is reached.

  As the organic metal salt flame retardant other than the fluorine-substituted organic sulfonic acid alkali (earth) metal salt, a metal salt of an organic sulfonic acid containing no fluorine atom is suitable. Examples of the metal salt include an alkali metal salt of an aliphatic sulfonic acid, an alkaline earth metal salt of an aliphatic sulfonic acid, an alkali metal salt of an aromatic sulfonic acid, and an alkaline earth metal salt of an aromatic sulfonic acid (any Also does not contain a fluorine atom).

  Preferable examples of the aliphatic sulfonic acid metal salt include an alkali (earth) metal salt of an alkyl sulfonate, and these can be used alone or in combination of two or more (here, alkali The (earth) metal salt is used to include both alkali metal salts and alkaline earth metal salts). Preferred examples of the alkane sulfonic acid used for the alkali (earth) metal salt of the alkyl sulfonate include methane sulfonic acid, ethane sulfonic acid, propane sulfonic acid, butane sulfonic acid, methyl butane sulfonic acid, hexane sulfonic acid, and heptane. Examples thereof include sulfonic acid and octanesulfonic acid, and these can be used alone or in combination of two or more.

  The aromatic sulfonic acid used in the aromatic (earth) metal salt of aromatic sulfonate includes monomeric or polymeric aromatic sulfide sulfonic acid, aromatic carboxylic acid and ester sulfonic acid, monomeric or polymeric sulfonic acid. Aromatic ether sulfonic acid, aromatic sulfonate sulfonic acid, monomeric or polymeric aromatic sulfonic acid, monomeric or polymeric aromatic sulfonic acid, aromatic ketone sulfonic acid, heterocyclic sulfonic acid, Examples include at least one acid selected from the group consisting of sulfonic acids of aromatic sulfoxides and condensates of methylene type bonds of aromatic sulfonic acids, and these are used alone or in combination of two or more. be able to.

  Specific examples of the aromatic (earth) metal salt of an aromatic sulfonate include, for example, disodium diphenyl sulfide-4,4′-disulfonate, dipotassium diphenyl sulfide-4,4′-disulfonate, potassium 5-sulfoisophthalate, Sodium 5-sulfoisophthalate, polysodium polyethylene terephthalate polysulfonate, calcium 1-methoxynaphthalene-4-sulfonate, disodium 4-dodecylphenyl ether disulfonate, polysodium poly (2,6-dimethylphenylene oxide) polysulfonate Poly (1,3-phenylene oxide) polysulfonic acid polysodium, poly (1,4-phenylene oxide) polysulfonic acid polysodium, poly (2,6-diphenylphenylene oxide) polysulfonic acid poly Lithium, poly (2-fluoro-6-butylphenylene oxide) polysulfonate, potassium sulfonate of benzenesulfonate, sodium benzenesulfonate, strontium benzenesulfonate, magnesium benzenesulfonate, dipotassium p-benzenedisulfonate, naphthalene-2 , 6-disulfonic acid dipotassium, biphenyl-3,3'-disulfonic acid calcium, diphenylsulfone-3-sulfonic acid sodium, diphenylsulfone-3-sulfonic acid potassium, diphenylsulfone-3,3'-disulfonic acid dipotassium, diphenylsulfone Α, α, α-trifluoroacetophenone sodium 4-sulfonate, dipotassium benzophenone-3,3′-disulfonate, Nene-2,5-disulfonate, dipotassium thiophene-2,5-disulfonate, calcium thiophene-2,5-disulfonate, sodium benzothiophenesulfonate, potassium diphenylsulfoxide-4-sulfonate, naphthalene Examples thereof include a formalin condensate of sodium sulfonate and a formalin condensate of sodium anthracene sulfonate.

  Among the metal salts of organic sulfonic acids that do not contain fluorine atoms, alkali (earth) metal salts of aromatic sulfonates are preferred, and potassium salts are particularly preferred. When blending the aromatic sulfonate alkali (earth) metal salt as a flame retardant, the content is preferably 0.01 to 1 part by weight based on 100 parts by weight of the total of the A component and the B component. More preferably, it is 0.05-0.8 weight part, More preferably, it is 0.08-0.6 weight part.

(E-3) Silicone-based flame retardant The silicone compound used as the silicone-based flame retardant of the present invention improves flame retardancy by a chemical reaction during combustion. As the compound, various compounds conventionally proposed as flame retardants for aromatic polycarbonate resins can be used. The silicone compound binds itself during combustion or binds to a component derived from the resin to form a structure, or imparts a flame retardant effect to the polycarbonate resin by a reduction reaction during the structure formation. It is considered. Therefore, it is preferable that a group having high activity in such a reaction is contained, and more specifically, a predetermined amount of at least one group selected from an alkoxy group and a hydrogen (ie, Si—H group) is contained. preferable. As a content rate of this group (alkoxy group, Si-H group), the range of 0.1-1.2 mol / 100g is preferable, the range of 0.12-1 mol / 100g is more preferable, 0.15-0. A range of 6 mol / 100 g is more preferable. Such a ratio can be determined by measuring the amount of hydrogen or alcohol generated per unit weight of the silicone compound by the alkali decomposition method. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, and particularly preferably a methoxy group.

Generally, the structure of a silicone compound is constituted by arbitrarily combining the following four types of siloxane units. That is,
M units: (CH ₃ ) ₃ SiO _1/2 , H (CH ₃ ) ₂ SiO _1/2 , H ₂ (CH ₃ ) SiO _1/2 , (CH ₃ ) ₂ (CH ₂ = CH) SiO _1/2 Monofunctional siloxane units such as (CH ₃ ) ₂ (C ₆ H ₅ ) SiO _1/2 , (CH ₃ ) (C ₆ H ₅ ) (CH ₂ ═CH) SiO _1/2 ,
D unit: (CH ₃ ) ₂ SiO, H (CH ₃ ) SiO, H ₂ SiO, H (C ₆ H ₅ ) SiO, (CH ₃ ) (CH ₂ ═CH) SiO, (C ₆ H ₅ ) ₂ SiO Bifunctional siloxane units such as
T unit: (CH ₃ ) SiO _3/2 , (C ₃ H ₇ ) SiO _3/2 , HSiO _3/2 , (CH ₂ ═CH) SiO _3/2 , (C ₆ H ₅ ) SiO _3/2 etc. A trifunctional siloxane unit of
Q unit: a tetrafunctional siloxane unit represented by SiO ₂ .

Specifically, the structure of the silicone compound used in the silicone-based flame retardant is represented by the following formulas: D _n , T _p , M _m D _n , M _m T _p , M _m Q _q , M _m D _n T _{p , M m D n Q q,} M m T p Q q, M m D n T p Q q, D n T p, D n Q q, include _{D n} T p _{Q q.} Among these, preferable structures of the silicone compound are M _m D _n , M _m T _p , M _m D _n T _p , and M _m D _n Q _q , and more preferable structures are M _m D _n or M _m D _n. T _p .

  Here, the coefficients m, n, p, and q in the above formulas are integers of 1 or more representing the degree of polymerization of each siloxane unit, and the sum of the coefficients in each formula is the average degree of polymerization of the silicone compound. . This average degree of polymerization is preferably in the range of 3 to 150, more preferably in the range of 3 to 80, still more preferably in the range of 3 to 60, and particularly preferably in the range of 4 to 40. The better the range, the better the flame retardancy. Further, as described later, a silicone compound containing a predetermined amount of an aromatic group is excellent in transparency and hue.

  When any of m, n, p, and q is a numerical value of 2 or more, the siloxane unit with the coefficient can be two or more types of siloxane units having different hydrogen atoms or organic residues to be bonded. .

  The silicone compound may be linear or have a branched structure. The organic residue bonded to the silicon atom is preferably an organic residue having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms. Specific examples of such an organic residue include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a decyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, And aralkyl groups such as tolyl groups. More preferably, they are a C1-C8 alkyl group, an alkenyl group, or an aryl group. As the alkyl group, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, and a propyl group is particularly preferable.

  Further, the silicone compound used as the silicone flame retardant preferably contains an aryl group. More preferably, the ratio (aromatic group amount) of the aromatic group represented by the following general formula (II) is 10 to 70% by weight (more preferably 15 to 60% by weight).

（式（ＩＩ）中、Ｘはそれぞれ独立にＯＨ基、炭素数１〜２０の一価の有機残基を示す。ｎは０〜５の整数を表わす。さらに式（ＩＩ）中においてｎが２以上の場合はそれぞれ互いに異なる種類のＸを取ることができる。）

(In formula (II), each X independently represents an OH group or a monovalent organic residue having 1 to 20 carbon atoms. N represents an integer of 0 to 5. Further, in formula (II), n is 2) In these cases, different types of X can be taken.)

  The silicone compound used as the silicone-based flame retardant may contain a reactive group in addition to the Si-H group and the alkoxy group. Examples of the reactive group include an amino group, a carboxyl group, an epoxy group, and a vinyl group. Examples thereof include a group, a mercapto group, and a methacryloxy group.

  As the silicone compound having a Si—H group, a silicone compound containing at least one of structural units represented by the following general formulas (III) and (IV) is preferably exemplified.

（式（ＩＩＩ）および式（ＩＶ）中、Ｚ^１〜Ｚ^３はそれぞれ独立に水素原子、炭素数１〜２０の一価の有機残基、または下記一般式（ＩＶ）で示される化合物を示す。α^１〜α^３はそれぞれ独立に０または１を表わす。ｍ１は０もしくは１以上の整数を表わす。さらに式（ＩＶ）中においてｍ１が２以上の場合の繰返し単位はそれぞれ互いに異なる複数の繰返し単位を取ることができる。）

(In formula (III) and formula (IV), Z ^{1 to} Z ³ each independently represent a hydrogen atom, a monovalent organic residue having 1 to 20 carbon atoms, or a compound represented by the following general formula (IV). Α ^{1 to} α ³ each independently represents 0 or 1. m1 represents 0 or an integer of 1 or more, and the repeating unit in the case where m1 is 2 or more in formula (IV) is a plurality of repeating units different from each other. Can take units.)

（式（Ｖ）中、Ｚ^４〜Ｚ^８はそれぞれ独立に水素原子、炭素数１〜２０の一価の有機残基を示す。α^４〜α^８はそれぞれ独立に０または１を表わす。ｍ２は０もしくは１以上の整数を表わす。さらに式（Ｖ）中においてｍ２が２以上の場合の繰返し単位はそれぞれ互いに異なる複数の繰返し単位を取ることができる。）

(In formula (V), Z ^{4 to} Z ⁸ each independently represents a hydrogen atom or a monovalent organic residue having 1 to 20 carbon atoms. Α ^{4 to} α ⁸ each independently represents 0 or 1. m 2 Represents 0 or an integer greater than or equal to 1. Further, in the formula (V), when m2 is 2 or more, the repeating unit can take a plurality of different repeating units.

  Examples of the silicone compound having an alkoxy group in the silicone compound used for the silicone-based flame retardant include at least one compound selected from compounds represented by the general formula (VI) and the general formula (VII).

（式（ＶＩ）中、β^１はビニル基、炭素数１〜６のアルキル基、炭素数３〜６のシクロアルキル基、並びに炭素数６〜１２のアリール基およびアラルキル基を示す。γ^１、γ^２、γ^３、γ^４、γ^５、およびγ^６は炭素数１〜６のアルキル基およびシクロアルキル基、並びに炭素数６〜１２のアリール基およびアラルキル基を示し、少なくとも１つの基がアリール基またはアラルキル基である。δ^１、δ^２、およびδ^３は炭素数１〜４のアルコキシ基を示す。）

(In the formula (VI), β ¹ represents a vinyl group, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group or aralkyl group having 6 to 12 carbon atoms. Γ ¹ , γ ² , γ ³ , γ ⁴ , γ ⁵ , and γ ⁶ represent an alkyl group and a cycloalkyl group having 1 to ⁶ carbon atoms, and an aryl group and an aralkyl group having 6 to 12 carbon atoms, and at least one group is aryl. And δ ¹ , δ ² , and δ ³ are each an alkoxy group having 1 to 4 carbon atoms.)

（式（ＶＩＩ）中、β^２およびβ^３はビニル基、炭素数１〜６のアルキル基、炭素数３〜６のシクロアルキル基、並びに炭素数６〜１２のアリール基およびアラルキル基を示す。γ^７、γ^８、γ^９、γ^１０、γ^１１、γ^１２、γ^１３およびγ^１４は炭素数１〜６のアルキル基、炭素数３〜６のシクロアルキル基、並びに炭素数６〜１２のアリール基およびアラルキル基を示し、少なくとも１つの基がアリール基またはアラルキルである。δ^４、δ^５、δ^６、およびδ^７は炭素数１〜４のアルコキシ基を示す。）

(In Formula (VII), β ² and β ³ represent a vinyl group, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group and an aralkyl group having 6 to 12 carbon atoms. γ ⁷ , γ ⁸ , γ ⁹ , γ ¹⁰ , γ ¹¹ , γ ¹² , γ ^13, and γ ¹⁴ are each an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and 6 to 12 carbon atoms. An aryl group and an aralkyl group, and at least one group is an aryl group or an aralkyl group, and δ ⁴ , δ ⁵ , δ ⁶ , and δ ⁷ represent an alkoxy group having 1 to 4 carbon atoms.

When using a silicone-based flame retardant as the flame retardant, the blending amount is preferably 0.1 to 5 parts by weight, more preferably 0.2 to 0.2 parts by weight based on a total of 100 parts by weight of the component A and the component B. 4 parts by weight, more preferably 0.3 to 3 parts by weight.
The flame retardants (E-1), (E-2) and (E-3) may be used alone or in combination of two or more.

(F component: Fluorine-containing anti-dripping agent)
The fluorine-containing anti-dripping agent (F component) used in the present invention is a fluorine-containing compound that prevents melt dripping during combustion and further improves flame retardancy, and is typically polytetrafluoro having fibril-forming ability. Ethylene is mentioned. Hereinafter, polytetrafluoroethylene may be simply referred to as PTFE. PTFE having a fibril forming ability has a very high molecular weight, and tends to be bonded to each other by an external action such as shearing force to form a fiber. The molecular weight is 1 million to 10 million, more preferably 2 million to 9 million in the number average molecular weight determined from the standard specific gravity. Such PTFE can be used in solid form or in the form of an aqueous dispersion. In addition, PTFE having such fibril-forming ability can improve the dispersibility in the resin, and it is also possible to use a PTFE mixture in a mixed form with other resins in order to obtain better flame retardancy and mechanical properties. is there.

  Examples of commercially available PTFE having such fibril forming ability include Teflon (registered trademark) 6J from Mitsui DuPont Fluorochemical Co., Ltd., Polyflon MPA FA500 from Daikin Chemical Industries, and F-201L. . Commercially available aqueous dispersions of PTFE include: Fullon AD-1, AD-936 manufactured by Asahi IC Fluoropolymers Co., Ltd. Fullon D-1, D-2 manufactured by Daikin Industries, Ltd., Mitsui DuPont Fluoro A typical example is Teflon (registered trademark) 30J manufactured by Chemical Corporation.

  As a mixed form of PTFE, (1) a method in which an aqueous dispersion of PTFE and an aqueous dispersion or solution of an organic polymer are mixed and co-precipitated to obtain a co-aggregated mixture (Japanese Patent Application Laid-Open No. 60-258263; (Method described in JP-A-63-154744), (2) A method of mixing an aqueous dispersion of PTFE and dried organic polymer particles (method described in JP-A-4-272957), (3) A method in which an aqueous dispersion of PTFE and an organic polymer particle solution are uniformly mixed, and each medium is simultaneously removed from the mixture (described in JP-A-06-220210, JP-A-08-188653, etc.) And (4) a method of polymerizing monomers forming an organic polymer in an aqueous dispersion of PTFE (a method described in JP-A-9-95583), and (5) A method in which an aqueous dispersion of TFE and an organic polymer dispersion are uniformly mixed, and then a vinyl monomer is further polymerized in the mixed dispersion, and then a mixture is obtained (described in JP-A-11-29679, etc.). Those obtained by (Method) can be used. Commercially available products of PTFE in these mixed forms include “Metablene A3800” (trade name) manufactured by Mitsubishi Rayon Co., Ltd. and “BLENDEX B449” (trade name) manufactured by GE Specialty Chemicals.

  As a ratio of PTFE in the mixed form, 1 to 60% by weight of PTFE is preferable in 100% by weight of the PTFE mixture, and more preferably 5 to 55% by weight. When the ratio of PTFE is within such a range, good dispersibility of PTFE can be achieved.

(About the content of each component)
In the polycarbonate resin composition of the present invention, the component A is 99 to 1% by weight, preferably 98 to 20% by weight, more preferably 97 to 40% by weight, particularly preferably 100% by weight in total of the component A and the component B. Is 95 to 60% by weight, B component is 1 to 99% by weight, preferably 2 to 80% by weight, more preferably 3 to 60% by weight, and particularly preferably 5 to 40% by weight.
If the component A is less than 1% by weight, the mechanical strength such as impact strength and heat resistance are insufficient, and if it exceeds 99% by weight, the moldability is lowered, which is not suitable.

  The content of component C is 0.1 to 10 parts by weight, preferably 0.5 to 9 parts by weight, and more preferably 1 to 8 parts by weight with respect to 100 parts by weight of the total of component A and component B. If it is less than 0.1 parts by weight, the generation of the flow line and the impact characteristics are insufficient, and if it exceeds 10 parts by weight, the heat resistance and flame retardancy are remarkably lowered, which is not suitable.

  The content of component D is preferably 0.1 to 50 parts by weight, more preferably 0.5 to 40 parts by weight, still more preferably 1 to 30 parts by weight with respect to 100 parts by weight of the total of component A and component B. It is. If the amount of the F component exceeds 50 parts by weight, the fluidity and impact strength are significantly reduced, which is not suitable.

  The content of component E is preferably 0.001 to 25 parts by weight, more preferably 0.05 to 23 parts by weight, and still more preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the total of component A and component B. Parts by weight. If it is less than 0.01 part by weight, the flame retardancy is insufficient, and if it exceeds 25 parts by weight, the heat resistance and mechanical strength are remarkably lowered, which is not suitable.

  The content of the component F is preferably 0.05 to 2 parts by weight, more preferably 0.07 to 1.5 parts by weight, still more preferably 0.1 to 0.1 parts by weight with respect to a total of 100 parts by weight of the component A and the component B. 1 part by weight. When the content of the E component is less than 0.01 parts by weight, the flame retardancy is insufficient, and when it exceeds 5 parts by weight, mechanical properties such as impact strength are deteriorated, which is not suitable.

(Other additives)
(I) Phosphorus stabilizer Examples of the phosphorous stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, and tertiary phosphine.

  Specifically, as the phosphite compound, for example, triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl Phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di -N-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, dis Allyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite, phenylbisphenol A Examples include pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, and dicyclohexyl pentaerythritol diphosphite.

  Further, as other phosphite compounds, those which react with dihydric phenols and have a cyclic structure can be used. For example, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert- Examples include butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite and 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite.

  Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, Examples thereof include diisopropyl phosphate, and triphenyl phosphate and trimethyl phosphate are preferable.

  Examples of the phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylenedi. Phosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite Tetrakis (2,6-di-tert-butylphenyl) -4,3′-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3′-biphenylene diphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl)- 4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, and the like, and tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite, bis (Di-tert-butylphenyl) -phenyl-phenylphosphonite is preferred, tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl)- More preferred is phenyl-phenylphosphonite. Such a phosphonite compound is preferable because it can be used in combination with a phosphite compound having an aryl group in which two or more alkyl groups are substituted.

  Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.

  Tertiary phosphine includes triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, tri-p-tolyl. Examples include phosphine, trinaphthylphosphine, and diphenylbenzylphosphine. A particularly preferred tertiary phosphine is triphenylphosphine.

  The phosphorus stabilizers can be used alone or in combination of two or more. Among the phosphorus stabilizers, phosphonite compounds or phosphite compounds represented by the following general formula (VIII) are preferable.

（式（ＶＩＩＩ）中、ＲおよびＲ’は炭素数６〜３０のアルキル基または炭素数６〜３０のアリール基を表し、互いに同一であっても異なっていてもよい。）

(In formula (VIII), R and R ′ represent an alkyl group having 6 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and may be the same as or different from each other.)

  As described above, tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite is preferable as the phosphonite compound, and the stabilizer containing phosphonite as a main component is Sandostab P-EPQ (trademark, manufactured by Clariant). ) And Irgafos P-EPQ (trademark, manufactured by CIBA SPECIALTY CHEMICALS) and both can be used.

  Among the above formulas (VIII), more preferred phosphite compounds are distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di). -Tert-butyl-4-methylphenyl) pentaerythritol diphosphite, and bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite.

  Distearyl pentaerythritol diphosphite is commercially available as ADK STAB PEP-8 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and JPP681S (trademark, manufactured by Johoku Chemical Industry Co., Ltd.), and any of them can be used. Bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite is ADK STAB PEP-24G (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.), Alkanox P-24 (trademark, manufactured by Great Lakes), Ultranox. P626 (trademark, manufactured by GE Specialty Chemicals), Doverphos S-9432 (trademark, manufactured by Dover Chemical), and Irgafos 126 and 126FF (trademark, manufactured by CIBA SPECIALTY CHEMICALS) are also available. Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is commercially available as ADK STAB PEP-36 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and can be easily used. Further, bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite is produced by ADK STAB PEP-45 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and Doverphos S-9228 (trademark). , Manufactured by Dober Chemical Co.) and any of them can be used.

(Ii) Hindered phenolic antioxidant As the hindered phenolic compound, various compounds that are usually blended in a resin can be used. Examples of such hindered phenol compounds include α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2-tert -Butyl-6- (3'-tert-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N, N-dimethylamino) Methyl) phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl) -6-tert-butylphenol), 4,4'-methylenebis (2,6 Di-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-dimethylene-bis (6-α-methyl-benzyl-p-cresol), 2,2 ′ -Ethylidene-bis (4,6-di-tert-butylphenol), 2,2'-butylidene-bis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert) -Butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6-hexanediol bis [3- (3,5-di- tert-butyl-4-hydroxyphenyl) propionate], bis [2-tert-butyl-4-methyl 6- (3-tert-butyl) Ru-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1, -Dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4'-thiobis (6-tert-butyl-m-cresol), 4,4'-thiobis (3- Methyl-6-tert-butylphenol), 2,2′-thiobis (4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4 ′ -Di-thiobis (2,6-di-tert-butylphenol), 4,4'-tri-thiobis (2,6-di-tert-butylphenol), 2,2-thiodie Renbis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-tert- Butylanilino) -1,3,5-triazine, N, N′-hexamethylenebis- (3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N, N′-bis [3- (3 , 5-Di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl -2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxyphenyl) iso Cyanurate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 1,3,5-tris2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, tetrakis [methylene-3- (3,5-di-tert-butyl- 4-hydroxyphenyl) propionate] methane, triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, triethylene glycol-N-bis-3- (3- tert-butyl-4-hydroxy-5-methylphenyl) acetate, 3,9-bis [2 {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) acetyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, tetrakis [Methylene-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] methane, 1,3,5-trimethyl-2,4,6-tris (3-tert-butyl-4-hydroxy Examples include -5-methylbenzyl) benzene and tris (3-tert-butyl-4-hydroxy-5-methylbenzyl) isocyanurate.

  Among the above compounds, tetrakis [methylene-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] methane, octadecyl-3- (3,5-di-tert-butyl-) is used in the present invention. 4-hydroxyphenyl) propionate, and 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4 , 8,10-Tetraoxaspiro [5,5] undecane is preferably used. In particular, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxa Spiro [5,5] undecane is preferred. The said hindered phenolic antioxidant can be used individually or in combination of 2 or more types.

  Either of the phosphorus stabilizer and the hindered phenol antioxidant is preferably blended, and the combination of these is more preferred. The compounding amount of the phosphorus stabilizer and the hindered phenol antioxidant is 0.001 to 3 parts by weight, preferably 0.005 to 2 parts by weight, more preferably 100 parts by weight in total of the A component and the B component. 0.01 to 1 part by weight. In the case of combined use, 0.01 to 0.3 parts by weight of a phosphorus-based stabilizer and 0.01 to 0.3 parts by weight of a hindered phenol-based antioxidant are added to 100 parts by weight of the total of component A and component B. More preferably, it is blended.

(Iii) Mold Release Agent The polycarbonate resin composition of the present invention preferably further contains a mold release agent for the purpose of improving productivity during molding and reducing distortion of the molded product. Known release agents can be used. For example, saturated fatty acid ester, unsaturated fatty acid ester, polyolefin wax (polyethylene wax, 1-alkene polymer, etc., which may be modified with a functional group-containing compound such as acid modification), silicone compound, fluorine compound ( And fluorine oil represented by polyfluoroalkyl ether), paraffin wax, beeswax and the like. Among these, fatty acid esters are preferable as a release agent. Such fatty acid esters are esters of aliphatic alcohols and aliphatic carboxylic acids. Such an aliphatic alcohol may be a monohydric alcohol or a dihydric or higher polyhydric alcohol. Moreover, as carbon number of this alcohol, it is the range of 3-32, More preferably, it is the range of 5-30. Examples of such monohydric alcohols include dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, seryl alcohol, and triacontanol. Examples of such polyhydric alcohols include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerol to hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, and mannitol. In the fatty acid ester of the present invention, a polyhydric alcohol is more preferable.

  On the other hand, the aliphatic carboxylic acid preferably has 3 to 32 carbon atoms, and particularly preferably an aliphatic carboxylic acid having 10 to 22 carbon atoms. Examples of the aliphatic carboxylic acid include decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, behenic acid, Mention may be made of saturated aliphatic carboxylic acids such as icosanoic acid and docosanoic acid, and unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid, and cetreic acid . Among the above, aliphatic carboxylic acids having 14 to 20 carbon atoms are preferable. Of these, saturated aliphatic carboxylic acids are preferred. In particular, stearic acid and palmitic acid are preferred.

  The above aliphatic carboxylic acids such as stearic acid and palmitic acid are usually produced from natural fats and oils such as animal fats such as beef tallow and lard and vegetable oils such as palm oil and sunflower oil. Therefore, these aliphatic carboxylic acids are usually a mixture containing other carboxylic acid components having different numbers of carbon atoms. Accordingly, in the production of the fatty acid ester of the present invention, aliphatic carboxylic acids produced from such natural fats and oils and in the form of a mixture containing other carboxylic acid components, particularly stearic acid and palmitic acid are preferably used.

  The fatty acid ester of the present invention may be either a partial ester or a total ester (full ester). However, partial esters are more preferably full esters because they usually have a high hydroxyl value and tend to induce decomposition of the resin at high temperatures. The acid value in the fatty acid ester of the present invention is preferably 20 or less, more preferably 4 to 20 and even more preferably 4 to 12 from the viewpoint of thermal stability. The acid value can be substantially zero. The hydroxyl value of the fatty acid ester is more preferably in the range of 0.1-30. Further, the iodine value is preferably 10 or less. The iodine value can be substantially zero. These characteristics can be obtained by a method defined in JIS K 0070.

  The content of the release agent is preferably 0.005 to 2 parts by weight, more preferably 0.01 to 1 part by weight, and still more preferably 0.05 to 0 parts per 100 parts by weight of the total of component A and component B. .5 parts by weight. In such a range, the polycarbonate resin composition has good release properties and release properties. In particular, such an amount of fatty acid ester provides a polycarbonate resin composition having good release properties and roll release properties without impairing good hue.

(Iv) Ultraviolet absorber The polycarbonate resin composition of the present invention may contain an ultraviolet absorber. Since the resin composition of the present invention is excellent in transparency, it is very suitable for use in transmitting light.
Specific examples of the ultraviolet absorber of the present invention include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4 in the benzophenone series. -Benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydridolate benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2, 2 ′, 4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-5-sodiumsulfoxybenzophenone, bis (5-Benzoyl-4-hydroxy-2- Examples include methoxyphenyl) methane, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2′-carboxybenzophenone.

  Specific examples of the ultraviolet absorber include, for example, 2- (2-hydroxy-5-methylphenyl) benzotriazole and 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole in the benzotriazole series. 2- (2-hydroxy-3,5-dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2′- Methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl) ) Benzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazol 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-5- tert-butylphenyl) benzotriazole, 2- (2-hydroxy-4-octoxyphenyl) benzotriazole, 2,2'-methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2'-p -Phenylenebis (1,3-benzoxazin-4-one), and 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole, and 2- (2'-Hydroxy-5-methacryloxyethylphenyl) -2H-benzotriazole and co-polymerized with the monomer 2 such as a copolymer with a possible vinyl monomer and a copolymer of 2- (2′-hydroxy-5-acryloxyethylphenyl) -2H-benzotriazole with a vinyl monomer copolymerizable with the monomer Examples include polymers having a -hydroxyphenyl-2H-benzotriazole skeleton.

  Specific examples of the ultraviolet absorber include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol and 2- (4) in hydroxyphenyltriazine series. , 6-Diphenyl-1,3,5-triazin-2-yl) -5-methyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-ethyloxy Phenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-propyloxyphenol, and 2- (4,6-diphenyl-1,3,5-triazine-2- Yl) -5-butyloxyphenol and the like. Furthermore, the phenyl group of the above exemplary compounds such as 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hexyloxyphenol is 2,4-dimethyl. Examples of the compound are phenyl groups.

  As the ultraviolet absorber, specifically, in the cyclic imino ester type, for example, 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2 ′-(4,4′-diphenylene) ) Bis (3,1-benzoxazin-4-one), 2,2 ′-(2,6-naphthalene) bis (3,1-benzoxazin-4-one) and the like.

  Further, as the ultraviolet absorber, specifically, for cyanoacrylate, for example, 1,3-bis-[(2′-cyano-3 ′, 3′-diphenylacryloyl) oxy] -2,2-bis [(2- Examples include cyano-3,3-diphenylacryloyl) oxy] methyl) propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl) oxy] benzene.

  Further, the ultraviolet absorber has a structure of a monomer compound capable of radical polymerization, whereby the ultraviolet-absorbing monomer and / or the light-stable monomer having a hindered amine structure, and an alkyl (meth) acrylate. A polymer type ultraviolet absorber obtained by copolymerization with a monomer such as may be used. Preferred examples of the UV-absorbing monomer include compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton, and a cyanoacrylate skeleton in the ester substituent of (meth) acrylate. The

  Of these, benzotriazoles and hydroxyphenyltriazines are preferred from the viewpoint of ultraviolet absorbing ability, and cyclic iminoesters and cyanoacrylates are preferred from the viewpoint of heat resistance and hue (transparency). You may use the said ultraviolet absorber individually or in mixture of 2 or more types.

  Content of a ultraviolet absorber is 0.01-2 weight part with respect to a total of 100 weight part of A component and B component, Preferably it is 0.03-2 weight part, More preferably, 0.02-1 weight part, More preferably, it is 0.05-0.5 weight part.

(V) Dye / pigment The polycarbonate resin composition of the present invention can further contain various dyes / pigments and can provide a molded product exhibiting various design properties. Since the polycarbonate resin composition of the present invention is excellent in transparency, it is extremely suitable for use in transmitting light. Therefore, for example, by adding a fluorescent brightening agent, the polycarbonate resin composition of the present invention is given a higher light transmittance and natural transparency, and a fluorescent brightening agent or other fluorescent dye that emits light is added. By blending, it is possible to impart a better design effect utilizing the luminescent color. Further, a polycarbonate resin composition which is finely colored with a very small amount of dye and pigment and has high transparency can also be provided.

  Examples of the fluorescent dye (including a fluorescent brightening agent) used in the present invention include a coumarin fluorescent dye, a benzopyran fluorescent dye, a perylene fluorescent dye, an anthraquinone fluorescent dye, a thioindigo fluorescent dye, and a xanthene fluorescent dye. And xanthone fluorescent dyes, thioxanthene fluorescent dyes, thioxanthone fluorescent dyes, thiazine fluorescent dyes, and diaminostilbene fluorescent dyes. Among these, coumarin fluorescent dyes, benzopyran fluorescent dyes, and perylene fluorescent dyes are preferable because they have good heat resistance and little deterioration during molding of the polycarbonate resin.

Examples of dyes other than the above bluing agents and fluorescent dyes include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as bitumen, perinone dyes, quinoline dyes, quinacridone And dyes such as dyes, dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes. Furthermore, the resin composition of this invention can mix | blend a metallic pigment, and can also obtain a better metallic color. As the metallic pigment, those having a metal film or a metal oxide film on various plate-like fillers are suitable.
The content of the dye / pigment is preferably 0.00001 to 1 part by weight and more preferably 0.00005 to 0.5 part by weight with respect to 100 parts by weight of the total of the A component and the B component.

(Vi) Other Heat Stabilizers The polycarbonate resin composition of the present invention may contain other heat stabilizers other than the phosphorus stabilizers and hindered phenol antioxidants. Such other heat stabilizers are preferably used in combination with any of these stabilizers and antioxidants, and particularly preferably used in combination with both. Examples of such other heat stabilizers include lactone stabilizers represented by the reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene (such stabilizers). Is described in detail in JP-A-7-233160). Such a compound is commercially available as Irganox HP-136 (trademark, manufactured by CIBA SPECIALTY CHEMICALS) and can be used. Furthermore, a stabilizer obtained by mixing the compound with various phosphite compounds and hindered phenol compounds is commercially available. For example, Irganox HP-2921 manufactured by the above company is preferably exemplified. In the present invention, such a premixed stabilizer can also be used. The blending amount of the lactone stabilizer is preferably 0.0005 to 0.05 parts by weight, more preferably 0.001 to 0.03 parts by weight with respect to 100 parts by weight of the total of the A component and the B component.

  Other stabilizers include sulfur-containing stabilizers such as pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. Illustrated. Such a stabilizer is particularly effective when the resin composition is applied to rotational molding. The amount of the sulfur-containing stabilizer is preferably 0.001 to 0.1 parts by weight, more preferably 0.01 to 0.08 parts by weight with respect to 100 parts by weight of the total of the A component and the B component.

(Vii) White pigment for high light reflection The polycarbonate resin composition of the present invention can be provided with a light reflection effect by blending a white pigment for high light reflection. As such a white pigment, a titanium dioxide (particularly titanium dioxide treated with an organic surface treating agent such as silicone) pigment is particularly preferred. The content of the white pigment for high light reflection is preferably 3 to 30 parts by weight, and more preferably 8 to 25 parts by weight with respect to 100 parts by weight of the total of the A component and the B component. Two or more kinds of white pigments for high light reflection can be used in combination.

(Viii) Other additives The polycarbonate resin composition of the present invention includes thermoplastic resins other than component A and component B, other flow modifiers, antibacterial agents, dispersants such as liquid paraffin, and photocatalytic antifouling agents. Further, a heat ray absorbent and a photochromic agent can be blended.
As the thermoplastic resin other than the A component and the B component, polymethyl methacrylate resin (PMMA resin), cyclic polyolefin resin, polylactic acid resin, polycaprolactone resin, thermoplastic fluororesin (for example, represented by polyvinylidene fluoride resin), In addition, polyolefin resins (polyethylene resin, polypropylene resin, etc.) are exemplified.

(Manufacture of polycarbonate resin composition)
Arbitrary methods are employ | adopted in order to manufacture the polycarbonate resin composition of this invention. For example, the A component to the F component and optionally other additives are sufficiently mixed using a premixing means such as a V-type blender, a Henschel mixer, a mechanochemical apparatus, an extrusion mixer, and then extruded granulated as necessary. There is a method of granulating such a premixed mixture using a vessel or a briquetting machine, then melt-kneading with a melt-kneader represented by a vent type twin screw extruder, and then pelletizing with a pelletizer.

  In addition, a method of supplying each component independently to a melt kneader represented by a vent type twin screw extruder, or a part of each component is premixed and then supplied to the melt kneader independently of the remaining components. The method of doing is also mentioned. Examples of a method of premixing a part of each component include a method of premixing components other than the component A in advance and then mixing the components with the polycarbonate resin of the component A or directly supplying them to an extruder.

  As a premixing method, for example, when a component having a powder form is included as the component A, a part of the powder and an additive to be blended are mixed to produce a master batch of the additive diluted with the powder. A method using a master batch can be mentioned. Furthermore, the method etc. which supply one component independently from the middle of a melt extruder are mentioned. In addition, when there exists a liquid thing in the component to mix | blend, what is called a liquid injection apparatus or a liquid addition apparatus can be used for supply to a melt extruder.

As the extruder, one having a vent capable of degassing moisture in the raw material and volatile gas generated from the melt-kneaded resin can be preferably used. From the vent, a vacuum pump is preferably installed for efficiently discharging generated moisture and volatile gas to the outside of the extruder. It is also possible to remove a foreign substance from the resin composition by installing a screen for removing the foreign substance mixed in the extrusion raw material in the zone in front of the extruder die. Examples of such a screen include a wire mesh, a screen changer, a sintered metal plate (such as a disk filter), and the like.
Examples of the melt kneader include a banbury mixer, a kneading roll, a single screw extruder, a multi-screw extruder having three or more axes, in addition to a twin screw extruder.

  The resin extruded as described above is directly cut into pellets, or after forming strands, the strands are cut with a pelletizer to be pelletized. When it is necessary to reduce the influence of external dust during pelletization, it is preferable to clean the atmosphere around the extruder. Furthermore, in the manufacture of such pellets, various methods already proposed for polycarbonate resin for optical disks are used to narrow the shape distribution of pellets, reduce miscuts, and reduce fine powder generated during transportation or transportation. In addition, it is possible to appropriately reduce bubbles (vacuum bubbles) generated inside the strands and pellets. By these prescriptions, it is possible to increase the molding cycle and reduce the occurrence rate of defects such as silver. Moreover, although the shape of a pellet can take common shapes, such as a cylinder, a prism, and a spherical shape, it is a cylinder more suitably. The diameter of such a cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and still more preferably 2 to 3.3 mm. On the other hand, the length of the cylinder is preferably 1 to 30 mm, more preferably 2 to 5 mm, and still more preferably 2.5 to 3.5 mm.

  Also, master pellets are prepared by previously melting and kneading the A component and the E component in a melt kneader so as to contain the high concentration E component of the present invention, and the master pellet is added to the remaining A component and other additions. The method of mixing with an agent and pelletizing with a melt kneader is mentioned.

(About a molded article made of the resin composition of the present invention)
The resin composition in the present invention can usually produce various products by injection molding the pellets obtained by the above-described method. In such injection molding, not only a normal molding method but also an injection compression molding, an injection press molding, a gas assist injection molding, a foam molding (including those by injection of a supercritical fluid), an insert molding, depending on the purpose as appropriate. A molded product can be obtained using an injection molding method such as in-mold coating molding, heat insulating mold molding, rapid heating / cooling mold molding, two-color molding, sandwich molding, and ultrahigh-speed injection molding. The advantages of these various molding methods are already widely known. In addition, either a cold runner method or a hot runner method can be selected for molding.

  Moreover, the resin composition in this invention can also be used in the form of various profile extrusion molded products, a sheet | seat, a film, etc. by extrusion molding. For forming sheets and films, an inflation method, a calendar method, a casting method, or the like can also be used. It is also possible to form a heat-shrinkable tube by applying a specific stretching operation. The resin composition of the present invention can be formed into a molded product by rotational molding, blow molding or the like.

  Specific examples of the molded product in which the resin composition of the present invention is used are suitable for application to internal parts and housings of OA equipment and home appliances. These products include, for example, personal computers, notebook computers, CRT displays, printers, mobile terminals, mobile phones, copiers, fax machines, recording media (CD, CD-ROM, DVD, PD, FDD, etc.) drives, parabolic antennas, electric motors. Tools, VTRs, TVs, irons, hair dryers, rice cookers, microwave ovens, audio equipment, audio equipment such as audio / laser discs / compact discs, lighting equipment, refrigerators, air conditioners, typewriters, word processors, etc. Resin products formed from the flame-retardant thermoplastic resin composition of the present invention can be used for various parts such as these cases. Examples of other resin products include vehicle parts such as deflector parts, car navigation parts, and car stereo parts.

  The polycarbonate resin composition of the present invention is widely useful in various OA applications and other fields because it does not have flow lines generated at welds and uneven thickness parts and is excellent in impact characteristics and moldability. Therefore, the industrial effect exhibited by the present invention is extremely great.

  The form of the invention that the present inventor considers to be the best is an aggregation of the preferable ranges of the above requirements. For example, typical examples are described in the following examples. Of course, the present invention is not limited to these forms.

The following examples further illustrate the present invention. Unless otherwise specified, parts in the examples are parts by weight, and% is% by weight. Evaluation was carried out by the following method.
(Evaluation of polycarbonate resin composition)
(I) Flame retardance According to UL standard 94V, a combustion test was performed at a thickness of 1.5 mm.
The flame retardance rank is preferably V-1 class or higher.
(Ii) Charpy impact strength According to ISO 179, measurement of Charpy impact strength with a notch was performed.
(Iii) Heat resistance The deflection temperature under load was measured in accordance with ISO 75-1 and 75-2. The measurement load was 1.80 MPa.
(Iv) Fluidity An Archimedean spiral flow length having a channel thickness of 2 mm and a channel width of 8 mm was measured with an injection molding machine [SG150U manufactured by Sumitomo Heavy Industries, Ltd.]. The cylinder temperature was 260 ° C., the mold temperature was 70 ° C., and the injection pressure was 98 MPa.
(V) Appearance (linear color unevenness)
1 to 3 are molded, and the linear color unevenness (flow line A) generated on the extended line of the weld portion and the linear color unevenness (flow) starting from the boss are formed. The presence or absence of line B) was confirmed.
○: No color unevenness
×: Color unevenness occurs

[Examples 1 to 19, Comparative Examples 1 to 10]
In the composition shown in Tables 1 to 3, the E component FR-1 (phosphate ester), the D component (reinforced filler), and the B component (ABS-1, ABS-2, ABS-3, ABS-4) The mixture consisting of the components to be removed was fed from the first feed port of the extruder. Such a mixture was obtained by mixing the following premix (i) with other components using a V-type blender. That is, (i) A mixture of an F component (fluorine-containing anti-dripping agent) and an A component aromatic polycarbonate, and the entire bag is shaken in a polyethylene bag so that the F component is 2.5% by weight. It is a mixture uniformly mixed with. When B component (ABS-1, ABS-2, ABS-3, ABS-4) and D component (reinforcement filler) were included, it supplied from the 2nd supply port using the side feeder. Furthermore, when adding FR-1 of E component, in the state heated to 80 degreeC, the 3rd supply port (1st in the middle of a cylinder using a liquid injection apparatus (HYM-JS-08 by Fuji Techno Industry Co., Ltd.)) was used. From the position between the supply port and the vent exhaust port), each was supplied to the extruder at a predetermined ratio. The liquid injection device was set to supply a constant amount, and the supply amounts of other raw materials were precisely measured with a measuring instrument [CWF manufactured by Kubota Corporation]. Extrusion is performed by using a vent type twin screw extruder (Nippon Steel Works TEX30α-38.5BW-3V) with a diameter of 30 mmφ, melt kneading at a screw speed of 150 rpm, a discharge rate of 20 kg / h, and a vent vacuum of 3 kPa. Pellets were obtained. In addition, about extrusion temperature, it implemented at 260 degreeC from the 1st supply port to the die part.

  A part of the obtained pellets was dried with a hot air circulation dryer at 80 to 90 ° C. for 6 hours and then used for evaluation test pieces (UL94, ISO179, ISO75-1 and ISO75-) using an injection molding machine. 2).

Each component represented by symbols in Tables 1 to 3 is as follows.
(A component)
PC-1 :: aromatic polycarbonate resin [polycarbonate resin powder having a viscosity average molecular weight of 22,500 made from bisphenol A and phosgene by a conventional method, Panlite L-1225WP manufactured by Teijin Chemicals Ltd.]
PC-2: Aromatic polycarbonate resin [polycarbonate resin powder having a viscosity average molecular weight of 19,700 made from bisphenol A and phosgene by a conventional method, Panlite L-1225WX manufactured by Teijin Chemicals Ltd.]

(B component)
ABS-1: ABS resin [manufactured by Nippon A & L Co., Ltd., Clarastic SXH-330 (trade name), butadiene rubber component about 17.5 wt%, weight average rubber particle size 0.40 μm, produced by emulsion polymerization]
ABS-2: ABS resin [manufactured by Nippon A & L Co., Ltd. UT-61 (trade name), butadiene rubber component about 14% by weight, weight average rubber particle size of 0.56 μm, manufactured by bulk polymerization]
ABS-5: ABS resin produced by an emulsion polymerization method (manufactured by CHEIL INDUSTRY INC .: CHT (trade name); the amount of rubber component comprising polybutadiene is about 58% by weight, and the weight average rubber particle size is 0.31 μm)

(C component)
MBS-1: Core-shell type graft copolymer [graft copolymer in which the core produced by emulsion polymerization is 70% by weight of butadiene rubber component and the shell is 30% by weight of styrene and methyl methacrylate, weight average of rubber component Particle size is 0.32μm]
MBS-2: Core-shell type graft copolymer [graft copolymer in which core produced by emulsion polymerization is 70% by weight of butadiene rubber component and shell is 30% by weight of styrene and methyl methacrylate, weight average of rubber component Particle size is 0.41 μm]
MBS-3: Core-shell type graft copolymer [Rohm and Haas Co., Ltd .: Paraloid EXL-2678 (trade name); graft copolymer in which core is 60% by weight of polybutadiene and shell is 40% by weight of styrene and methyl methacrylate Polymer, weight average particle size of 0.35 μm, produced by emulsion polymerization]

(D component)
WSN: Wollastonite (manufactured by Shimizu Kogyo; H-1250F (trade name))
Talc: Talc (Made by Hayashi Kasei Co., Ltd .; HST0.8 (trade name))
Mica: Mascobite (manufactured by Yamaguchi Mika Kogyo Co., Ltd .; A-41 (trade name))

(E component)
FR-1: Phosphate ester mainly composed of bisphenol A bis (diphenyl phosphate) (manufactured by Daihachi Chemical Industry Co., Ltd .: CR-741 (trade name))
FR-2: potassium perfluorobutanesulfonate (manufactured by Dainippon Ink & Chemicals, Inc., MegaFuck F-114P (trade name))
FR-3: organosiloxane flame retardant containing Si-H group, methyl group and phenyl group (X-40-2600J (trade name) manufactured by Shin-Etsu Chemical Co., Ltd.)

(F component)
PTFE: Polytetrafluoroethylene (manufactured by Daikin Industries, Ltd., Polyflon MP FA500C (trade name))

(Other ingredients)
ABS-3: ABS resin produced by an emulsion polymerization method (the amount of rubber component made of polybutadiene is about 15% by weight, and the weight average rubber particle size is 0.18 μm)
ABS-4: ABS resin produced by an emulsion polymerization method (the amount of rubber component made of polybutadiene is about 21% by weight, and the weight average rubber particle size is 2.2 μm)
MBS-4: Core-shell graft copolymer (Mitsubishi Rayon Co., Ltd .: Methbrene C-223A (trade name); Graft copolymer with 70% by weight of polybutadiene core and styrene and methyl methacrylate as the core, weight average Particle size is 0.23μm)
MBS-5: Core-shell type graft copolymer [graft copolymer in which the core produced by emulsion polymerization is 70% by weight of butadiene rubber component and the shell is 30% by weight of styrene and methyl methacrylate, weight average of rubber component Particle size is 0.55μm]
DC30M: Olefin wax by copolymerization of α-olefin and maleic anhydride (Mitsubishi Chemical Co., Ltd .; Diacarna 30M (trade name))
SL900: Fatty acid ester release agent (Riken Vitamin Co., Ltd .; Riquemar SL900 (trade name))
IRGX: Phenol-based heat stabilizer (Ciba Specialty Chemicals KK; IRGANOX 1076 (trade name))
TMP: Phosphate heat stabilizer (manufactured by Daihachi Chemical Industry Co., Ltd .; TMP (trade name))

  By using the diene rubber having a specific weight average particle diameter of the present invention from the above table, a polycarbonate having both an excellent appearance without a flow line generated at the weld and uneven thickness portions, and excellent impact characteristics and moldability. It can be seen that a resin composition can be obtained.

BRIEF DESCRIPTION OF THE DRAWINGS It is a front-side perspective schematic diagram of the molded article which imitated the housing of the notebook computer used in the Example (length 178 mm × width 245 mm × edge height 10 mm, thickness 2.0 mm). The molded product has two side gates (length 5 mm × width 8 mm, thickness 1.5 mm). It is the surface side front schematic diagram of the molded article used in the Example, and shows a gate position, a flow line generation place, and an expected weld position. It is a back side front schematic diagram of the molded product used in the example, and shows a state where there is a ribbed boss. (Boss shape: 6.5 mm outer diameter, 2.5 mm inner diameter, 10 mm height)

Explanation of symbols

1 Molded product body that mimics the housing of a notebook computer 2 Mirror surface part 3 Matte surface part 4 Gate (2 side gates, length 5 mm x width 8 mm, thickness 1.5 mm)
5 Weld expected position 6 Flow line A (Linear color unevenness starting from the part considered to be weld)
7 Flow line B (Linear color unevenness generated in the resin flow direction starting from the boss)
8 Ribbed boss (Outer diameter is 6.5mm, Inner diameter is 2.5mm, Height is 10mm)

Claims (8)

  An aromatic polycarbonate resin (component A) 99 to 1% by weight, a rubbery polymer having a rubber particle weight average particle diameter of 0.20 to 2.0 μm, a vinyl cyanide monomer and an aromatic vinyl monomer Alkyl (meth) acrylate in the presence of a diene rubber component having a weight average particle size of 0.30 to 0.50 μm with respect to a total of 100 parts by weight of the graft copolymer (component B) 1 to 99% by weight A core-shell type graft copolymer (component C) obtained by copolymerizing a monomer or a mixture of an alkyl (meth) acrylate monomer and a monomer copolymerizable therewith by an emulsion polymerization method is 0.1 to A polycarbonate resin composition containing 10 parts by weight.   The polycarbonate resin composition according to claim 1, wherein the graft copolymer (component B) is a graft copolymer obtained by emulsion polymerization and containing 1 to 40% by weight of a diene rubber as a rubbery polymer.   The polycarbonate resin composition according to claim 1 or 2, wherein the core-shell type graft copolymer (component C) is a core-shell type graft copolymer containing 40 to 90% by weight of a diene rubber component.   The polycarbonate resin composition according to any one of claims 1 to 3, comprising 0.1 to 50 parts by weight of an inorganic filler (D component) with respect to 100 parts by weight of the total of the A component and the B component.   The polycarbonate resin composition according to any one of claims 1 to 4, wherein the inorganic filler (component D) is at least one selected from the group consisting of talc, mica, and wollastonite.   One or more flame retardants (E component) selected from the group consisting of phosphate esters, alkali (earth) sulfonates, and silicone compounds with respect to a total of 100 parts by weight of component A and component B The polycarbonate resin composition according to any one of claims 1 to 5, comprising 001 to 25 parts by weight and 0.05 to 2 parts by weight of a fluorine-containing anti-dripping agent (component F). The polycarbonate resin composition according to any one of claims 1 to 6, wherein the flame retardant (E component) is a phosphate ester represented by the following formula (I).

(X in the formula is hydroquinone, resorcinol, bis (4-hydroxydiphenyl) methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone and bis (4 -Hydroxyphenyl) a dihydric phenol residue derived from a dihydroxy compound selected from the group consisting of sulfides, n is an integer from 0 to 5, or in the case of a mixture of n different phosphate esters, R ⁴ , R ⁵ , R ⁶ , and R ⁷ are average values each derived from an aryl group selected from the group consisting of independent phenol, cresol, xylenol, isopropylphenol, butylphenol, and p-cumylphenol. Residual phenol Group.)   The molded object shape | molded with the polycarbonate resin composition of any one of Claims 1-7.

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